Effective Novel Non-Polymeric and Non-Fouling Additive for Inhibiting High-Temperature Naphthenic Acid Corrosion and Method of Using the Same

ABSTRACT

The present invention relates to inhibition of high temperature naphthenic acid corrosion occurring in hydrocarbon processing units. The invention provides an effective novel non-polymeric and non-fouling additive for inhibiting high-temperature naphthenic acid corrosion, comprising an effective corrosion-inhibiting amount of a second phosphate ester wherein said second phosphate ester is obtained by reacting a first phosphate ester with an oxirane compound selected from the group consisting of butylene oxide, ethylene oxide, propylene oxide or any other oxirane compound or a combination thereof, preferably with butylene oxide, capably yielding said second phosphate ester, having a structure A or B, 
     
       
         
         
             
             
         
       
     
     wherein R 1  and R 2  are each independently selected from the group consisting of moieties having 1 to 20 carbon atoms and R 1  and R 2  may be identical or different, X is H, CH 3  or C 2 H 5 ; and n may vary from 1 to 20,
 
wherein said first phosphate ester is having a structure I or II,
 
     
       
         
         
             
             
         
       
     
     wherein R 1  and R 2  are each independently selected from the group consisting of moieties having 1 to 20 carbon atoms and R 1  and R 2  may be identical or different, said first phosphate ester being obtained as a reaction product of reaction of an alcohol with a phosphorous pentaoxide.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a filing under 35 U.S.C. 371 of InternationalApplication No. PCT/IB2010/051636 filed Apr. 15, 2010 entitled “AnEffective Novel Non-Polymeric and Non-Fouling Additive for InhibitingHigh-Temperature Naphthenic Acid Corrosion and Method of Using theSame,” claiming priority of Indian Patent Application No. 974/MUM/2009filed Apr. 15, 2009, which applications are incorporated by referenceherein in their entirety.

FIELD OF THE INVENTION

The present invention relates to the inhibition of metal corrosion inacidic hot hydrocarbons and particularly to the inhibition of corrosionof iron-containing metals in hot acidic hydrocarbons, especially whenthe acidity is derived from the presence of naphthenic acid and moreparticularly to an effective non-polymeric and non-fouling additive toeffect corrosion inhibition and a method of using the same.

BACKGROUND

It is widely known in the art that the processing of crude oil and itsvarious fractions causes damage to piping and other associated equipmentdue to naphthenic acid corrosion. These are corrosive to the equipmentused for distillation, extraction, transportation and processing of thecrudes. Generally speaking, naphthenic acid corrosion occurs when thecrude being processed has a neutralization number or total acid number(TAN), expressed as the milligrams of potassium hydroxide required toneutralize the acids in one gram sample, above 0.2. It is also knownthat naphthenic acid-containing hydrocarbon is at a temperature betweenabout 200° C. and 400° C. (approximately 400° F.-750° F.), the fluidvelocities are high and liquid impinges on process surfaces e.g. intransfer lines, return bends and restricted flow areas.

Corrosion problems in petroleum refining operations associated withnaphthenic acid constituents and sulfur compounds in crude oils havebeen recognized for many years. Such corrosion is particularly severe inatmospheric and vacuum distillation units at temperatures between 400°F. and 790° F. Other factors that contribute to the corrosivity ofcrudes containing naphthenic acids include the amount of naphthenic acidpresent, the concentration of sulfur compounds, the velocity andturbulence of the flow stream in the units, and the location in the unit(e.g., liquid/vapor interface).

As commonly used, naphthenic acid is a collective term for certainorganic acids present in various crude oils. Although there may bepresent minor amounts of other organic acids, it is understood that themajority of the acids in naphthenic based crude are naphthenic incharacter, i.e., with a saturated ring structure as follows:

The molecular weight of naphthenic acid can extend over a large range.The majority of the naphthenic acid from crude oils is found in gas oiland light lubricating oil. When hydrocarbons containing such naphthenicacids come in contact with iron-containing metals, especially atelevated temperatures, severe corrosion problems arise.

Naphthenic acid corrosion has plagued the refining industry for manyyears. This corroding material consists of predominantly monocyclic orbicyclic carboxylic acids with a boiling range between 350° and 650° F.These acids tend to concentrate in the heavier fractions during crudedistillation. Thus, locations such as the furnace tubing, transferlines, fractionating tower internals, feed and reflux sections ofcolumns, heat exchangers, tray bottoms and condensers are primary sitesof attack by naphthenic acid. Additionally, when crude stocks high innaphthenic acids are processed, severe corrosion can occur in the carbonsteel or ferritic steel furnace tubes and tower bottoms. Recently muchinterest has grown in the control of this type of corrosion inhydrocarbon processing units due to the presence of naphthenic acid incrudes from locations such as China, India, Africa and Europe.

Crude oils are hydrocarbon mixtures which have a range of molecularstructures and consequent range of physical properties. The physicalproperties of naphthenic acids which may be contained in the hydrocarbonmixtures also vary with the changes in molecular weight, as well as thesource of oil containing the acid. Therefore, characterization andbehavior of these acids are not well understood. A well known methodused to “quantify” the acid concentration in crude oil has been a KOHtitration of the oil. The oil is titrated with KOH, a strong base, to anend point which assures that all acids in the sample have beenneutralized. The unit of this titration is milligrams of KOH/gram ofsample and is referred to as the “Total Acid Number” (TAN) orNeutralization Number. Both terms are used interchangeably in theapplication.

The unit of TAN is commonly used since it is not possible to calculatethe acidity of the oil in terms of moles of acid, or any other of theusual analytical terms for acid content. Refiners have used TAN as ageneral guideline for predicting naphthenic acid corrosion. For example,many refineries blend their crude to a TAN=0.5 assuming that at theseconcentrations naphthenic acid corrosion will not occur. However, thismeasure has been unsuccessful in preventing corrosion by naphthenicacid.

Naphthenic acid corrosion is highly temperature dependent. The generallyaccepted temperature range for this corrosion is between 205° C. and400° C. (400° F. and 750° F.). Corrosion attack by these acids below205° C. has not yet been reported in the published literature. As to theupper boundary, data suggests that corrosion rates reach a maximum atabout 600°-700° F. and then begin to diminish.

The concentration and velocity of the acid/oil mixture are alsoimportant factors which influence naphthenic acid corrosion. This isevidenced by the appearance of the surfaces affected by naphthenic acidcorrosion. The manner of corrosion can be deduced from the patterns andcolor variations in the corroded surfaces. Under some conditions, themetal surface is uniformly thinned. Thinned areas also occur whencondensed acid runs down the wall of a vessel. Alternatively, in thepresence of naphthenic acid, pitting occurs often in piping or at welds.Usually the metal outside the pit is covered with a heavy, black sulfidefilm, while the surface of the pit is bright metal or has only a thin,grey to black film covering it. Moreover, another pattern of corrosionis erosion-corrosion, which has a characteristic pattern of gouges withsharp edges. The surface appears clean, with no visible by-products. Thepattern of metal corrosion is indicative of the fluid flow within thesystem, since increased contact with surfaces allows for a greateramount of corrosion to take place. Therefore, corrosion patterns provideinformation as to the method of corrosion which has taken place. Also,the more complex the corrosion, i.e., in increasing complexity fromuniform to pitting to erosion-corrosion, the lower is the TAN valuewhich triggers the behavior.

The information provided by corrosion patterns indicates whethernaphthenic acid is the corroding agent, or rather if the process ofcorrosion occurs as a result of attack by sulfur. Most crude's containhydrogen sulfide, and therefore readily form iron sulfide films oncarbon steel. In all cases that have been observed in the laboratory orin the field, metal surfaces have been covered with a film of some sort.In the presence of hydrogen sulfide the film formed is invariably ironsulfide, while in the few cases where tests have been run in sulfur freeconditions, the metal is covered with iron oxide, as there is alwaysenough water or oxygen present to produce a thin film on the metalcoupons.

Tests utilized to determine the extent of corrosion may also serve asindicators of the type of corrosion occurring within a particularhydrocarbon treating unit. Metal coupons can be inserted into thesystem. As they are corroded, they lose material. This weight loss isrecorded in units of mg/cm.sup.2. Thereafter, the corrosion rate can bedetermined from weight loss measurements. Then the ratio of corrosionrate to corrosion product (mpy/mg/cm.sup.2) is calculated. This is afurther indicator of the type of corrosion process which has takenplace, for example, if this ratio is less than 10, it has been foundthat there is little or no contribution of naphthenic acid to thecorrosion process. However, if the ratio exceeds 10, then naphthenicacid is a significant contributor to the corrosion process.

Distinguishing between sulfidation attack and corrosion caused bynaphthenic acid is important, since different remedies are requireddepending upon the corroding agent. Usually, retardation of corrosioncaused by sulfur compounds at elevated temperatures is effected byincreasing the amount of chromium in the alloy which is used in thehydrocarbon treating unit. A range of alloys may be employed, from 1.25%Cr to 12% Cr, or perhaps even higher. Unfortunately, these show littleto no resistance to naphthenic acid. To compensate for the corrodingeffects of sulfur and naphthenic acid, an austenitic stainless steelwhich contains at least 2.5% molybdenum, must be utilized. The corrosionproblem is known to be aggravated by the elevated temperatures,necessary to refine and crack the oil and by the oil's acidity which iscaused primarily by high levels of naphthenic acid indigenous to thecrudes. Naphthenic acids are corrosive between the ranges of about 175°C. to 420° C. At higher temperatures the naphthenic acids are in thevapor phase and at the lower temperatures the corrosion rate is notserious. The corrosivity of naphthenic acids appears to be exceptionallyserious in the presence of sulfide compounds, such as hydrogen sulfide,mercaptans, elemental sulfur, sulfides, disulfides, polysulfides andthiophenols. Corrosion due to sulfur compounds becomes significant attemperatures as low as 450° F. The catalytic generation of hydrogensulfide by thermal decomposition of mercaptans has been identified as acause of sulfidic corrosion.

Sulfur in the crudes, which produces hydrogen sulfide at highertemperatures, also aggravates the problem. The temperature range ofprimary interest for this type of corrosion is in the range of fromabout 175° C. to about 400° C., especially about 205° C. to about 400°C.

Various approaches to controlling naphthenic acid corrosion haveincluded neutralization and/or removal of naphthenic acids from thecrude being processed; blending low acid number oils with corrosive highacid number oils to reduce the overall neutralization number; and theuse of relatively expensive corrosion-resistant alloys in theconstruction of the piping and associated equipment. These attempts aregenerally disadvantageous in that they require additional processingand/or add substantial costs to treatment of the crude oil.Alternatively, various amine and amide based corrosion inhibitors arecommercially available, but these are generally ineffective in the hightemperature environment of naphthenic acid corrosion. Naphthenic acidcorrosion is readily distinguished from conventional fouling problemssuch as coking and polymer deposition which can occur in ethylenecracking and other hydrocarbon processing reactions using petroleumbased feedstocks. Naphthenic acid corrosion produces a characteristicgrooving of the metal in contact with the corrosive stream. In contrast,coke deposits generally have corrosive effects due to carburization,erosion and metal dusting.

Because these approaches have not been entirely satisfactory, theaccepted approach in the industry is to construct the distillation unit,or the portions exposed to naphthenic acid/sulfur corrosion, with theresistant metals such as high quality stainless steel or alloyscontaining higher amounts of chromium and molybdenum. The installationof corrosion-resistant alloys is capital intensive, as alloys such as304 and 316 stainless steels are several times the cost of carbon steel.However, in units not so constructed there is a need to provideinhibition treatment against this type of corrosion. The prior artcorrosion inhibitors for naphthenic acid environments includenitrogen-based filming corrosion inhibitors. However, these corrosioninhibitors are relatively ineffective in the high temperatureenvironment of naphthenic acid oils.

While various corrosion inhibitors are known in various prior arts, theefficacy and usefulness of any particular corrosion inhibitor isdependent on the circumstances in which it is applied. Thus, efficacy orusefulness under one set of circumstances often does not imply the samefor another set of circumstances. As a result, a large number ofcorrosion inhibitors have been developed and are in use for applicationto various systems depending on the medium treated, the type of surfacethat is susceptible to the corrosion, the type of corrosion encountered,and the conditions to which the medium is exposed. For example, U.S.Pat. No. 3,909,447 describes certain corrosion inhibitors as usefulagainst corrosion in relatively low temperature oxygenated aqueoussystems such as water floods, cooling towers, drilling muds, airdrilling and auto radiator systems. That patent also notes that manycorrosion inhibitors capable of performing in non-aqueous systems and/ornon-oxygenated systems perform poorly in aqueous and/or oxygenatedsystems. The reverse is true as well. The mere fact that an inhibitorthat has shown efficacy in oxygenated aqueous systems does not suggestthat it would show efficacy in a hydrocarbon. Moreover, the mere factthat an inhibitor has been efficacious at relatively low temperaturesdoes not indicate that it would be efficacious at elevated temperatures.In fact, it is common for inhibitors that are very effective atrelatively low temperatures to become ineffective at temperatures suchas the 175° C. to 400° C. encountered in oil refining. At suchtemperatures, corrosion is notoriously troublesome and difficult toalleviate. Thus, U.S. Pat. No. 3,909,447 contains no teaching orsuggestion that it would be effective in non-aqueous systems such ashydrocarbon fluids, especially hot hydrocarbon fluids. Nor is there anyindication in U.S. Pat. No. 3,909,447 that the compounds disclosedtherein would be effective against naphthenic acid corrosion under suchconditions.

Atmospheric and vacuum distillation systems are subject to naphthenicacid corrosion when processing certain crude oils. Currently usedtreatments are thermally reactive at use temperatures. In the case ofphosphorus-based inhibitors, this is thought to lead to a metalphosphate surface film. The film is more resistant to naphthenic acidcorrosion than the base steel. These inhibitors are relatively volatileand exhibit fairly narrow distillation ranges. They are fed into acolumn above or below the point of corrosion depending on thetemperature range. Polysulfide inhibitors decompose into complexmixtures of higher and lower polysulfides and, perhaps, elemental sulfurand mercaptans. Thus, the volatility and protection offered is notpredictable.

The problems caused by naphthenic acid corrosion in refineries and theprior art solutions to those problems have been described at length inthe literature, the following of which are representative:

U.S. Pat. No. 3,531,394 to Koszman described the use of phosphorusand/or bismuth compounds in the cracking zone of petroleum steamfurnaces to inhibit coke formation on the furnace tube walls.

U.S. Pat. No. 4,024,049 to Shell et al disclosed compounds for use asrefinery antifoulants. While effective as antifoulant materials,materials of this type have not heretofore been used as corrosioninhibitors in the manner set forth herein. While this reference teachesthe addition of thiophosphate esters such as those used in the subjectinvention to the incoming feed, due to the non-volatile nature of theester materials they do not distill into the column to protect thecolumn, the pump-around piping, or further process steps.

U.S. Pat. No. 4,105,540 to Weinland described phosphorus containingcompounds as antifoulant additives in ethylene cracking furnaces. Thephosphorus compounds employed are mono- and di-esters of phosphate andphosphite compounds having at least one hydrogen moiety complexed withan amine.

U.S. Pat. No. 4,443,609 disclosed certain tetrahydrothiazole phosphonicacids and esters as being useful as acid corrosion inhibitors. Suchinhibitors can be prepared by reacting certain 2,5-dihydrothiazoles witha dialkyl phosphite. While these tetrahydrothiazole phosphonic acids oresters have good corrosion and inhibition properties, they tend to breakdown during high temperature applications thereof with possible emissionof obnoxious and toxic substances.

It is also known that phosphorus-containing compounds impair thefunction of various catalysts used to treat crude oil, e.g., infixed-bed hydrotreaters and hydrocracking units. Crude oil processorsare often in a quandary since if the phosphite stabilizer is not used,then iron can accumulate in the hydrocarbon up to 10 to 20 ppm andimpair the catalyst. Although nonphosphorus-containing inhibitors arecommercially available, they are generally less effective than thephosphorus-containing compounds.

U.S. Pat. No. 4,542,253 to Kaplan et al, described a method of reducingfouling and corrosion in ethylene cracking furnaces using petroleumfeedstocks including at least 10 ppm of a water soluble amine complexedphosphate, phosphite, thiophosphate or thiophosphite ester compound,wherein the amine has a partition coefficient greater than 1.0 (equalsolubility in both aqueous and hydrocarbon solvents).

U.S. Pat. No. 4,842,716 to Kaplan et al described a method for reducingfouling and corrosion by using at least 10 ppm of a combination of aphosphorus antifoulant compound and a filming inhibitor. The phosphoruscompound is a phosphate, phosphite, thiophosphate or thiophosphite estercompound. The filming inhibitor is an imidazoline compound.

U.S. Pat. No. 4,941,994 Zetmeisl et al disclosed a naphthenic acidcorrosion inhibitor comprising a dialkyl or trialkylphosphite incombination with an optional thiazoline.

U.S. Pat. No. 4,941,994 disclosed that metal corrosion in hot acidicliquid hydrocarbons is inhibited by the presence of a corrosioninhibiting amount of a dialkyl and/or trialkyl phosphite with anoptional thiazoline. Nevertheless, there is always a desire to enhancethe ability of corrosion inhibitors while reducing the amount ofphosphorus-containing compounds which may impair the function of variouscatalysts used to treat crude oil, as well as a desire for suchinhibitors that may be produced from lower cost or more availablestarting materials.

Another approach to the prevention of naphthenic acid corrosion is theuse of a chemical agent to form a barrier between the crude and theequipment of the hydrocarbon processing unit. This barrier or filmprevents corrosive agents from reaching the metal surface, and isgenerally a hydrophobic material. Gustaysen et al., in NACE Corrosion 89meeting, paper no. 449, Apr. 17-21, 1989 detail the requirements for agood filming agent. U.S. Pat. No. 5,252,254 discloses one such filmforming agent, sulfonated alkyl-substituted phenol, and claims effectiveprotecting against naphthenic acid corrosion.

U.S. Pat. No. 5,182,013 issued to Petersen et al. on Jan. 26, 1993described another method of inhibiting naphthenic acid corrosion ofcrude oil, comprising introducing into the oil an effective amount of anorganic polysulfide. This is another example of a corrosion-inhibitingsulfur species. Sulfidation as a source of corrosion was detailed above.Though the process is not well understood, it has been determined thatwhile sulfur can be an effective anti-corrosive agent in smallquantities, at sufficiently high concentrations, it becomes a corrosioncausing agent.

Organic polysulfides (Babaian-Kibala, U.S. Pat. No. 5,552,085), organicphosphites (Zetlmeisl, U.S. Pat. No. 4,941,994), and phosphate/phosphiteesters (Babaian-Kibala, U.S. Pat. No. 5,630,964), have been claimed tobe effective in hydrocarbon-rich phase against naphthenic acidcorrosion. However, their high oil solubility incurs the risk ofdistillate side stream contamination by phosphorus compounds. It can beseen from U.S. Pat. No. 5,630,964 that untreated phosphate esters arenot effective in corrosion-inhibition, (as can be seen from Tables 1 and2 of said patent). In this patent, effective corrosion-inhibition isachieved by a compound which is a combination of polysulphide anduntreated phosphate ester.

Phosphoric acid has been used primarily in aqueous phase for theformation of a phosphate/iron complex film on steel surfaces forcorrosion inhibition or other applications (Coslett, British patent8,667, U.S. Pat. Nos. 3,132,975, 3,460,989 and 1,872,091). Use ofphosphoric acid in high temperature non-aqueous environments (petroleum)has also been reported for purposes of fouling mitigation (U.S. Pat. No.3,145,886).

There remains a continuing need to develop innovative options formitigating the corrosivity of acidic crudes at lower cost. This isespecially true at times of low refining margins and a high availabilityof corrosive crudes from sources such as Europe, China, Africa, andIndia. The present invention addresses this need.

In view of above, there is a need to provide alternative additivecomposition which is non-fouling and less acidic to provide effectivehigh temperature naphthenic acid corrosion inhibition, which willovercome the disadvantages of the prior art compositions.

SUMMARY

The present invention provides an effective novel non-polymeric andnon-fouling additive for inhibiting high-temperature naphthenic acidcorrosion, comprising an effective corrosion-inhibiting amount of asecond phosphate ester wherein said second phosphate ester is obtainedby reacting a first phosphate ester with an oxirane compound selectedfrom the group consisting of butylene oxide, ethylene oxide, propyleneoxide or any other oxirane compound or a combination thereof, preferablywith butylene oxide, capably yielding said second phosphate ester,having a structure A or B,

wherein R¹ and R² are each independently selected from the groupconsisting of moieties having 1 to 20 carbon atoms and R¹ and R² may beidentical to or different from each other, X is H, CH₃ or C₂H₅; and nmay vary from 1 to 20,wherein said first phosphate ester is having a structure I or II,

wherein R¹ and R² are each independently selected from the groupconsisting of moieties having 1 to 20 carbon atoms and R¹ and R² may beidentical to or different from each other, said first phosphate esterbeing obtained as a reaction product of reaction of an alcohol with aphosphorous pentaoxide.

DESCRIPTION OF THE INVENTION

The present invention uses the following reacted compound to be used ascorrosion inhibitor for inhibiting high temperature naphthenic acidcorrosion. This reacted compound is obtained by reaction of alcohol withphosphorous pentoxide followed by reaction with oxirane compoundsselected from the group consisting of butylene oxides ethylene oxidesand propylene oxides and other such compounds.

The mole ratio of P₂O₅ to alcohol is preferably 1 mole of P₂O₅ to 1 to10 mole of alcohol and preferably 1 mole of P₂O₅ to 1 to 7 mole ofalcohol.

It has been surprisingly discovered by the inventor of the presentinvention, that a phosphate ester, reacted by oxirane compounds such asbutylene oxide are having lower phosphorus content, low acidity and, andnon-fouling nature and gives very effective and improved control ofnaphthenic acid corrosion, as compared with use of only non-treatedphosphate ester.

The novel additive is made in two basic steps.

-   -   1. Alcohol is reacted with phosphorus pentoxide. (The resulting        reaction compound is a commercially used prior art additive used        in inhibition of naphthenic acid corrosion). The reaction can be        carried out by using various mole ratios of alcohol and        phosphorus pentoxide. The resultant reaction compound is a        phosphate ester. This reaction compound is highly acidic in        nature.    -   2. The resultant reaction-compound, of step 1 is further reacted        with oxirane compounds like butylene oxide. Alternatively, the        other common oxides like ethylene oxide or propylene oxide or        any other oxirane compound also can be used. The resultant        reaction compound obtained after this step no. 2 is        butylene-oxide-treated phosphate ester.

It should be noted that during synthesis of phosphate esters, whereinalcohol and phosphorous pentaoxide are used, the resulting compoundcontains a mixture of mono-, di-, and tri-phosphate and many otherphosphorous compounds are formed. Typical structures I & II,respectively, of mono- and di-phosphate ester are shown below.

wherein R¹ and R² are each independently selected from the groupconsisting of moieties having 1 to 20 carbon atoms and R¹ and R² may beidentical to or different from each other.

This mixture predominantly contains mono- and di-phosphates and otherphosphorous compounds which are acidic in nature and expected to takepart in reaction with the oxirane compounds like butylene oxide,ethylene oxide and propylene oxide capably yielding phosphate ester.Typical structures A or B, respectively, of mono- and di-phosphate esterreacted with oxides are shown below

wherein R¹ and R² are each independently selected from the groupconsisting of moieties having 1 to 20 carbon atoms and R¹ and R² may beidentical to or different from each other, X is H, CH₃ or C₂H₅; and nmay vary from 1 to 20.

It should be noted that the above mentioned steps can be understoodbetter by referring to the corresponding examples.

The present invention is directed to a method for inhibiting corrosionon the metal surfaces of the processing units which process hydrocarbonssuch as crude oil and its fractions containing naphthenic acid. Theinvention is explained in details in its simplest form wherein thefollowing method steps are carried out, when it is used to process crudeoil in process units such as distillation unit. Similar steps can beused in different processing units such as, pump-around piping, heatexchangers and such other processing units.

These method steps are explained below:

-   -   a) heating the hydrocarbon containing naphthenic acid to        vaporize a portion of the hydrocarbon:    -   b) allowing the hydrocarbon vapors to rise in a distillation        column;    -   c) condensing a portion of the hydrocarbon vapours passing        through the distillation column to produce a distillate;    -   d) adding to the distillate, from 1 to 2000 ppm of, for example,        butylene-oxide-treated phosphate ester, which is the required        additive of present invention;    -   e) allowing the distillate containing additive compound of        step (d) to contact substantially the entire metal surfaces of        the distillation unit to form protective film on such surface,        whereby such surface is inhibited against corrosion.

It is advantageous to treat distillation column, trays, pump-aroundpiping and related equipment to prevent naphthenic acid corrosion, whencondensed vapours from distilled hydrocarbon fluids contact metallicequipment at temperatures greater than 200° C., and preferably 400° C.The additive is generally added to the condensed distillate and thecondensed distillate is allowed to contact the metallic surfaces of thedistillation column, packing, trays, pump around piping and relatedequipment as the condensed distillate passes down the column and intothe distillation vessel. The distillate may also be collected asproduct. The corrosion inhibitors of the instant invention remain in theresultant collected product.

In commercial practice, the additives of this invention may be added toa distillate return to control corrosion in a draw tray and in thecolumn packing while a second injection may be added to a spray oilreturn immediately below the draw trays to protect the tower packing andtrays below the distillate draw tray. It is not so critical where theadditive of the invention is added as long as it is added to distillatethat is later returned to the distillation vessel, or which contact themetal interior surfaces of the distillation column, trays, pump aroundpiping and related equipments.

EXAMPLES

The method of using the additive of the present invention for achievinginhibition of high temperature naphthenic acid corrosion is explainedbelow with the help of examples and tables.

Example 1

Into a clean four-necked round bottom flask, kept in an oil bath at 30°C., 733.4 gm of 2-ethyl-hexanol was charged, and nitrogen gas purgingwas started. Total amount of 266.5 gm of phosphorous pentoxide was addedto the flask in six installments. Exotherm was observed after additionof phosphorous pentoxide to the flask. After addition of phosphorouspentoxide was completed, the temperature of reaction mixture was raisedto 99° C. and this temperature was maintained for four hours.

The reaction mixture was cooled to 30° C.-35° C., filtered and analyzedfor acid value and phosphorous content by method of Inductive CoupledPlasma (ICP).

The acid value was found to be in the range of 280 to 330 mg KOH/gm.Typical acid value was 308 mg KOH/gm. The phosphorous content was in therange of 10 to 12%. Typical value of phosphorous content was 11.65%. Theresulting reaction mixture of Example 1 is prior art's additive forNaphthenic Acid Corrosion Inhibition. The results of experiments ofExample 1 are given in Table 1.

Example 2

Into a clean four-necked round bottom flask, kept in an oil bath at 30°C., 200 gm of reaction mixture of Example 1 was charged. Into thisreaction mixture 150 gm of butylene oxide was slowly added. The exothermwas observed and the temperature was maintained below 40° C. till theaddition of entire quantity of 150 gm of butylene oxide was completed.The samples of resulting chemical mixture were taken intermittently andwere analyzed for acid value. The reaction was continued till the acidvalue was 10 mg KOH/gm.

The resulting reaction mixture was then heated to 60° C. temperature,and was maintained at this temperature for two hours.

The resulting reaction mixture was cooled to 30° C.-35° C., filtered andanalyzed for acid value and phosphorous content, by method of ICP.

The acid value was found to be less than 10 mg KOH/gm. Typical acidvalue was 1 mg KOH/gm. The phosphorous content was in the range of 5 to7%. Typical phosphorous content value was 6.53%. The resulting reactionmixture of Example 2 is used as Invention-Additive for Naphthenic AcidCorrosion Inhibition. The results of experiments of Example 2 are givenin Table 1.

Example 3

Into a clean four-necked round bottom flask, kept in a water bath at 30°C., 486 gm of 2-ethyl-hexanol was charged, and nitrogen gas purging wasstarted. Total amount of 265 gm of phosphorous pentoxide was added tothe flask in six installments. Exotherm was observed after addition ofphosphorous pentoxide to the flask. After addition of phosphorouspentoxide was completed, the temperature of reaction mixture was raisedto 99° C. and this temperature was maintained for four hours.

The reaction mixture was cooled to room temperature of 30° C., filteredand analyzed for acid value and phosphorous content by method of ICP.

The acid value was found to be in the range of 320 to 350 mg KOH/gm.Typical acid value was 331 mg KOH/gm. The phosphorous content was in therange of 14 to 16%. Typical value of phosphorous content was 15.408%.The resulting reaction mixture of Example 3 is prior art's additive forNaphthenic Acid Corrosion Inhibition. The results of experiments ofExample 3 are given in Table 1.

Example 4

Into a clean four-necked round bottom flask, kept in a water bath at 30°C., 100 gm of reaction mixture of Example 3 was charged. Into thisreaction mixture 88 gm of butylene oxide was slowly added. The exothermwas observed and the temperature was maintained below 40° C. till theaddition of entire quantity of 88 gm of butylene oxide was completed.The samples of resulting chemical mixture were taken intermittently andwere analyzed for acid value. The reaction was continued till the acidvalue was 10 mg KOH/gm.

The resulting reaction mixture was then heated to 60° C. temperature,and was maintained at this temperature for two hours.

The resulting reaction mixture was cooled to room temperature of 30° C.,filtered and analyzed for acid value and phosphorous content, by ICP.

The acid value was found to be less than 10 mg KOH/gm. Typical acidvalue was 6.8 mg KOH/gm. The phosphorous content was in the range of 7to 9%. Typical phosphorous content value was 8.19%. The resultingreaction mixture of Example 4 is used as Invention-Additive forNaphthenic Acid Corrosion Inhibition. The results of experiments ofExample 4 are given in Table 1.

Example 5 High Temperature Naphthenic Acid Corrosion Test

In this example, various amounts of additives prepared in accordance,with Examples 1 to 4, were tested for corrosion inhibition efficiency onsteel coupons in a hot oil containing naphthenic acid. A weight losscoupon, immersion test was used to evaluate the invention compound forits effectiveness in inhibition of naphthenic acid corrosion at 290° C.temperature. Different dosages of invention additive compounds are usedas shown in Table 1.

A static test on steel coupon was conducted without using any additive.This test provided a blank test reading.

The reaction apparatus consisted of a one-litre four-necked round bottomflask equipped with water condenser, N₂ purger tube, thermometer pocketwith thermometer and stirrer rod. 600 gm (about 750 ml) paraffinhydrocarbon oil (D-130) with fractions boiling above 290° C., was takenin the flask. N₂ gas purging was started with flow rate of 100 cc/minuteand the temperature was raised to 100° C., which temperature wasmaintained for 30 minutes.

In different experiments, additive compounds of Examples 1 to 4 wereused for testing their effectiveness in Naphthenic Acid CorrosionInhibition. The reaction mixture after addition of additive compound wasstirred for 15 minutes at 100° C. temperature. After removing thestirrer, the temperature of the reaction mixture was raised to 290° C. Apre-weighed weight-loss carbon steel coupon CS 1010 with dimensions 76mm×13 mm×1.6 mm was immersed. After maintaining this condition for 1hour to 1.5 hours, 31 gm of naphthenic acid (commercial grade with acidvalue of 230 mg KOH/gm) was added to the reaction mixture. A sample ofone gm weight of reaction mixture was collected for determination ofacid value, which was found to be approximately 11.7. This condition wasmaintained for four hours. After this procedure, the metal coupon wasremoved, excess oil was rinsed away, and the excess corrosion productwas removed from the metal surface. Then the metal coupon was weighedand the corrosion rate was calculated in mils per year.

Calculation of Corrosion Inhibition Efficiency

The method used in calculating Corrosion Inhibition Efficiency is givenbelow. In this calculation, corrosion inhibition efficiency provided byadditive compound is calculated by comparing weight loss due to additivewith weight loss of blank coupon (without any additive).

${{Corrosion}\mspace{14mu} {Inhibition}\mspace{14mu} {Efficiency}} = {\frac{\begin{matrix}{\left( {{Weight}\mspace{14mu} {loss}\mspace{14mu} {for}\mspace{14mu} {blank}\mspace{14mu} {without}\mspace{14mu} {additive}} \right) -} \\\left( {{weight}\mspace{14mu} {loss}\mspace{14mu} {with}\mspace{14mu} {additive}} \right)\end{matrix}}{\left( {{weight}\mspace{14mu} {loss}\mspace{14mu} {for}\mspace{14mu} {blank}\mspace{14mu} {without}\mspace{14mu} {additive}} \right)} \times 100}$

The calculated magnitudes are entered in the Table 1 in appropriatecolumns.

Example 6 High Temperature Naphthenic Acid Corrosion Dynamic Test

The dynamic testing was carried out by using rotating means provided inthe temperature-controlled autoclave and was carried out by using steelcoupons. A weight-loss coupon immersion dynamic test was used toevaluate the invention compound for its effectiveness in inhibition ofnaphthenic acid corrosion at 260° C. temperature under dynamiccondition. In this example, various amounts of an about 50% or neatadditive prepared in accordance with Examples 1 to 4 were tested. Adynamic test on steel coupon was conducted without using any additive.This test provided a blank test reading.

The following test equipment and materials were used in the DynamicCorrosion Test:

-   -   1. Temperature controlled autoclave    -   2. Pre-weighed weight-loss carbon steel coupons CS 1010 with        dimensions 76 mm×13 mm×1.6 mm.    -   3. Means to rotate the coupon.

Material:

-   -   1. Naphthenic acid was externally added to provide an acid        neutralization number of approximately 12 mg/KOH/gm.    -   2. Nitrogen gas in the vapour space.

Two pre-weighed carbon steel coupons, were clamped to the rotating meansof the autoclave. The dynamic test was conducted at about 260° C. forabout 6 hours. After the test, the coupons were removed, excess oil wasrinsed away, excess corrosion product was removed from the surface ofcoupons. The coupons were then weighed and the corrosion rate wascalculated as mils/year. The results of this dynamic test are presentedin Table 2.

TABLE 1 Resulting Reaction Typical Additive Additive Product Phospho-Total Active Weight % from rous Dosage Dosage Loss in Effi- ExampleContent % (ppm) (ppm) mg MPY ciency Example 1 11.65 100 100 10.9 55 86.4(Prior art) 50 50 42.3 212 47.4 Example 2 6.53 75 75 3.4 17 95.8(Invention 50 50 13.8 69 82.8 Additive) Example 3 15.408 100 100 7.1 3691.2 (Prior Art) 50 50 39.9 200 50.4 Example 4 8.19 50 50 5.9 30 92.7(Invention 25 25 25.2 126 68.7 Additive) Blank 0 0 0 80.4 402 NA

TABLE 2 AUTOCLAVE TEST (Example 6) Additive Additive Active Mg TotalActive Typical Phospho- loss MPY % Dosage Dosage Phosphorous rous, afterafter efficiency Product (ppm) ppm content (%) ppm* test test after testBlank — — — 43.1 143.8 — Example 1 500 500 11.65 58.25 9.3 31.0 76.1Example 2 500 500 6.53 32.65 3.1 10.34 92.8 Example 3 500 500 15.4077.04 7.25 24.2 83.2 Example 4 500 500 8.19 40.95 1.4 4.7 96.7 Example 4250 250 8.19 20.48 3.67 12.24 91.5 Tributyl 500 500 11.6 58.0 38.05 12711.7 Phosphate Tris 2 Ethyl 500 500 7.0 35 40.89 136.4 5.10 HexylPhosphate *The column indicates active phosphorous in the system

Example 7 Fouling Tendency Of Corrosion Inhibiting Additives

The fouling tendency of each of invention additives and prior artadditives was determined by heating 1% solution of each additive in theoil at 290° C. for two hours. The observations with respect toprecipitate-formation are given in Table 3.

TABLE 3 Observation with respect Additive to precipitate - formationExample 1 Heavy precipitation Example 2 Slight solids - formationExample 3 Heavy precipitation Example 4 Slight solids - formationTributyl Phosphate Completely hazy solutionDetailed Discussion about Experimental Results

The detailed discussion given below, with respect to the experimentalresults, presented in Tables 1 to 3, for different experiments describedin Examples 1 to 6, explains the high effectiveness of the inventionadditive compound of present invention, in high temperature naphthenicacid corrosion inhibition. The inventor of the present invention hassurprisingly found that, even with reduction in amount of dosages usedof the active components of invention additive compound as compared withthe amount of dosages of prior art additive compounds, higheffectiveness in corrosion inhibition is obtained.

Detailed Discussion of Experimental Results Given in Table 1

It is seen that in Examples 1 and 3, wherein prior art additivecompounds were used, with active dosage amounts of 100 ppm of additivecompound, in each case, having typical phosphorous content percentage of11.65 and 15.408, respectively and the percent efficiency ofcorrosion-inhibition was respectively 86.4 and 91.2. In the sameexamples, by reducing the active dosage amounts to 50 ppm of additivecompound in each case with same percentages of phosphorous contentsmentioned above, the corresponding percentage efficiency of corrosioninhibition, dropped down respectively to 47.4 and 50.4.

While comparing the above mentioned results about effectiveness of priorart additives, it is seen in Examples 2 and 4, wherein inventionadditive compounds are used for naphthenic acid corrosion inhibition,that higher corrosion inhibition efficiencies are obtained by usinglower dosage amounts, also providing lesser percentages of phosphorouscontents, as shown below.

In Example 2, along with providing lesser percent phosphorous content of6.53, in each case, use of active dosage amounts of invention additivecompound of 75 ppm and 50 ppm, the corresponding percentage efficienciesof common inhibition were respectively 95.8 and 85.8.

In Example 4, along with providing a little higher percent phosphorouscontent of 8.19, in each case, with use of even reduced active dosageamounts of invention additive compound of 50 ppm and 25 ppm, thecorresponding percent efficiencies of corrosion inhibition wererespectively 92.7 and 68.7 respectively.

Detailed Discussion of Experimental Results Given in Table 2

It is seen that by using procedures of Examples 1 and 3, wherein priorart additive compounds were used with active dosage amounts of 500 ppmof additive compound, in each case, the typical phosphorous contentpercentage was respectively 11.65 and 15.408, and the percent efficiencyof corrosion-inhibition was respectively 76.1 and 83.2.

It is also seen that, by using prior art additive compound of tributylphosphate, with active dosage amount of 500 ppm, with typicalphosphorous content of 11.6%, the percent efficiency of corrosioninhibition was only 11.7%.

Similarly, it is seen that, by using prior art additive compound of Tris2 ethyl hexyl phosphate, with active dosage amount of 500 ppm withtypical phosphorous content of 7%, the percent efficiency of commoninhibition was only 5.1%.

While comparing the above mentioned results about effectiveness of priorart additives it is seen by using procedures of Examples 2 and 4,wherein invention additive compounds were used for naphthenic acidcorrosion inhibition, that higher corrosion inhibition efficiencies of92.8% and 96.7% respectively were obtained by using same active dosageamounts of 500 ppm in each case, along with percentages of typicalphosphorous contents, of 6.53% and 8.19% respectively.

By using procedure of Example 4 along with providing a percent oftypical phosphorous content of 8.19, with use of even reduced activedosage amount of 250 ppm of invention additive compound, thecorresponding percent efficiency of corrosion inhibition was 91.5%.

Detailed Discussion of Experimental Results Given in Table 3

Referring to Table 3, it is clearly seen from results of Examples 2 and4, that use of invention additive compounds led to very slightsolid-formation, whereas in case of Examples 1 and 3, use of prior artadditive compounds additive compounds led to heavy precipitation, whichcould lead to heavy fouling of equipments. Similarly use of prior artadditive of tributyl phosphate also led to completely hazy solution.

All of these details discussed above clearly point out to the fact that,as compared to additive compounds of prior art, the invention additivecompound of the present invention provides better efficiency ofcorrosion inhibition along with lower percent phosphorous content (andhence lower acidic value) and lower dosages of active invention additivecompound (thereby making it more economical). The invention additivecompound is also non-fouling as it leads to very slightsolids-formation.

Discussion of Distinguishing Features of Present Invention

Thus, it is seen that the additive compound of present invention usedfor corrosion-inhibition has the following important distinguishingfeatures, as compared to the prior art.

-   -   1) The inventor of the present invention, after extensive        experimentation, has surprisingly found that the additive        compound used by the inventor, is highly effective in high        temperature corrosion inhibition, as shown by the experimental        results given in Tables 1 and 2.    -   2) Another distinguishing feature of the additive compound of        present invention is that, it has very low acidity as compared        to the additive compounds of prior art, for example, the        phosphate esters of prior art has very high acidity. The        phosphate esters of prior art are known to have a tendency to        decompose, even at lower temperatures, to form phosphoric acids,        which travel further along the hydrocarbon stream and react with        metal surfaces of equipments such as packing of distillation        column, to form solid iron phosphate. These solids plug the        holes of equipments and thereby lead to fouling of distillation        column (refer to Table 3).    -    The additive compound of the present invention does not have        this deficiency.    -   3) The invention compound is very effective in        corrosion-inhibition, even when used in much lower dosage        amounts, as compared to the prior art compounds.    -   4) The corrosion-inhibition-efficiency is achieved by present        invention-additive, at low-phosphorous-concentrations (as        compared to prior art additives). This is very advantageous        because the phosphorous is poisonous for the performance of        catalysts used in further downstream units.    -   5) The invention compound has extremely low potential for        fouling as explained in the Table 3.    -   6) The invention-additive is shown to perform much better by        giving higher efficiencies as compared to other prior art        additives like trialkyl phosphates such as tributyl phosphate,        tris 2 ethyl hexyl phosphate.    -   7) The invention compound is a low-cost        corrosion-inhibiting-additive, as compared to prior art        additive.

It may be noted that effectiveness of present invention inhibitors hasbeen checked for crude oil containing naphthenic acid, but these aresuitable for crude oil containing naphthenic acid and sulfur compounds.

In view of the above, it is understood that, the present inventioncomprises of the following items:

Item 1: An effective novel non-polymeric and non-fouling additive forinhibiting high-temperature naphthenic acid corrosion, comprising aneffective corrosion-inhibiting amount of a second phosphate esterwherein said second phosphate ester is obtained by reacting a firstphosphate ester with an oxirane compound selected from the groupconsisting of butylene oxide, ethylene oxide, propylene oxide or anyother oxirane compound or a combination thereof, preferably withbutylene oxide, capably yielding said second phosphate ester, having astructure A or B,

wherein R¹ and R² are each independently selected from the groupconsisting of moieties having 1 to 20 carbon atoms and R¹ and R² may beidentical to or different from each other, X is H, CH₃ or C₂H₅; and nmay vary from 1 to 20,wherein said first phosphate ester is having a structure I or II,

wherein R¹ and R² are each independently selected from the groupconsisting of moieties having 1 to 20 carbon atoms and R¹ and R² may beidentical to or different from each other, said first phosphate esterbeing obtained as a reaction product of reaction of an alcohol with aphosphorous pentaoxide.Item 2: An effective additive, as described in item 1, wherein saideffective additive has acidity varying from about 1 mg KOH/gm to about20 mg KOH/gm as determined by titration of samples against normalalcoholic KOH.Item 3: An effective additive, as described in item 1, wherein saideffective additive has phosphorus contents varying from about 0.5% toabout 9% of said effective additive.Item 4: An effective additive, as described in item 1, wherein moleratios of said phosphorus pentoxide and said alcohol are used, such thatthe mole ratio of said phosphorus pentoxide to said alcohol ispreferably 1 mole of said phosphorus pentoxide to 1 to 10 mole of saidalcohol and preferably 1 mole of said phosphorus pentoxide to 1 to 7mole of said alcohol.Item 5: An effective additive as described in item 1, wherein activedosage of said additive is 1 to 2000 ppm.Item 6: A process of high temperature naphthenic acid corrosioninhibition of metallic surfaces of any of the hydrocarbon processingunits of a petrochemical plant, used for processing a stream containingnaphthenic acid, with said processing units comprising distillationcolumns, strippers, trays, pump around piping and related equipments,and said process using said second phosphate ester of item 1, comprisingthe steps of:

-   -   a. heating said hydrocarbon containing naphthenic acid to        vapourize a portion of said hydrocarbon;    -   b. condensing a portion of the hydrocarbon vapors, passing        through said hydrocarbon processing unit, to produce a condensed        distillate;    -   c. adding to said distillate, before said condensed distillate        is returned to said hydrocarbon processing unit or collected as        a product, from 1 to 2000 ppm of said second phosphate ester of        item 1 in corrosion-inhibition-effective-amount, capably forming        a reaction mixture;    -   d. allowing said reaction mixture to contact said metallic        surfaces of said hydrocarbon processing unit to form a        protective film on said surfaces whereby each of said surfaces        is inhibited against corrosion; and    -   e. allowing said condensed distillate to return to said        hydrocarbon processing unit, or to be collected as said product.        Item 7: A process as described in item 1, wherein said stream        includes crude oil, feedstock, and hydrocarbon stream and/or        fractions thereof.

The present invention has been described with reference to foregoingexamples. It is obvious for the person skilled in the art to modifythese without deviating from its scope, which are intended to beincluded within its scope.

1. An effective novel non-polymeric and non-fouling additive forinhibiting high-temperature naphthenic acid corrosion, comprising aneffective corrosion-inhibiting amount of an oxide treated phosphateester which is obtained by process comprising steps of: (a) reacting analcohol with phosphorus pentoxide resulting in a reaction mixture ofmono-, di-, and tri-phosphate esters and other phosphorous compoundspredominantly comprising acidic mono- and di-phosphate esters,respectively having structural formulae I and II

characterized in that (b) the resulted reaction mixture of step (a) isfurther reacted with an oxirane compound selected from butylene oxide,ethylene oxide, propylene oxide or any other oxirane compound or acombination thereof yielding said oxide treated phosphate ester,predominantly comprising mixture of compounds of structural formulae Aand B,

wherein R¹ and R² are each independently selected from the groupconsisting of moieties having 1 to 20 carbon atoms, and R¹ and R² may beidentical to or different from each other, X is H, CH₃ or C₂H₅; and nmay vary from 1 to
 20. 2. An effective additive, as claimed in claim 1,wherein said effective additive has acidity varying from about 1 mgKOH/gm to about 20 mg KOH/gm as determined by titration of samplesagainst normal alcoholic KOH.
 3. An effective additive, as claimed inclaim 1, wherein said effective additive has phosphorus contents varyingfrom about 0.5% to about 9% of said effective additive.
 4. An effectiveadditive, as claimed in claim 1, wherein mole ratios of said phosphoruspentoxide and said alcohol are used, such that the mole ratio of saidphosphorus pentoxide to said alcohol is 1 mole of said phosphoruspentoxide to 1 to 10 mole of said alcohol and 1 mole of said phosphoruspentoxide to 1 to 7 mole of said alcohol.
 5. An effective additive asclaimed in claim 1, wherein active dosage of said additive is from 1 to2000 ppm.
 6. A process of high temperature naphthenic acid corrosioninhibition of metallic surfaces of a hydrocarbon processing unit of apetrochemical plant, used for processing a stream containing naphthenicacid, with said processing units comprising distillation columns,strippers, trays, pump around piping and related equipments, and saidprocess using said oxide treated phosphate ester of claim 1, comprisingthe steps of: (a) heating said hydrocarbon containing naphthenic acid tovapourize a portion of said hydrocarbon; (b) condensing a portion of thehydrocarbon vapors, passing through said hydrocarbon processing unit, toproduce a condensed distillate; (c) adding to said distillate, beforesaid condensed distillate is returned to said hydrocarbon processingunit or collected as a product, from 1 to 2000 ppm of said oxide treatedphosphate ester of claim 1 in corrosion-inhibition-effective-amount,capably forming a reaction mixture; (d) allowing said reaction mixtureto contact said metallic surfaces of said hydrocarbon processing unit toform a protective film on said surfaces whereby each of said surfaces isinhibited against corrosion; and (e) allowing said condensed distillateto return to said hydrocarbon processing unit, or to be collected assaid product.
 7. A process as claimed in claim 6, wherein said streamincludes crude oil, feedstock, and hydrocarbon stream and/or fractionsthereof. 8-9. (canceled)
 10. An effective novel non-polymeric andnon-fouling additive for inhibiting high-temperature naphthenic acidcorrosion, comprising an effective corrosion-inhibiting amount of anoxide treated phosphate ester which is obtained by process comprisingsteps of: (a) reacting an alcohol with phosphorus pentoxide resulting ina reaction mixture of mono-, di-, and tri-phosphate esters and otherphosphorous compounds predominantly comprising acidic mono- anddi-phosphate esters, respectively having structural formulae I and II

characterized in that (b) the resulted reaction mixture of step (a) isfurther reacted with an oxirane compound selected from butylene oxide,ethylene oxide, propylene oxide or any other oxirane compound or acombination thereof yielding said oxide treated phosphate esterpredominantly comprising mixture of compounds of structural formulae Aand B,

wherein R¹ and R² are each independently selected from the groupconsisting of moieties having 1 to 20 carbon atoms, and R¹ and R² may beidentical to or different from each other, X is H, CH₃ or C₂H₅; and nis
 1. 11. An effective additive, as claimed in claim 10, whereinbutylene oxide treated phosphate ester comprises a mixture of compoundsof structural formulae A1 and B1,


12. A process of high temperature naphthenic acid corrosion inhibitionof metallic surfaces of a hydrocarbon processing unit of a petrochemicalplant, used for processing a stream containing naphthenic acid, withsaid processing unit comprising distillation columns, strippers, trays,pump around piping and related equipments, and said process using saidoxide treated phosphate ester of claim 11, comprising the steps of: (a)heating said hydrocarbon containing naphthenic acid to vapourize aportion of said hydrocarbon; (b) condensing a portion of the hydrocarbonvapors, passing through said hydrocarbon processing unit, to produce acondensed distillate; (c) adding to said distillate, before saidcondensed distillate is returned to said hydrocarbon processing unit orcollected as a product, from 1 to 2000 ppm of said oxide treatedphosphate ester of claim 11 in corrosion-inhibition-effective-amount,capably forming a reaction mixture; (d) allowing said reaction mixtureto contact said metallic surfaces of said hydrocarbon processing unit toform a protective film on said surfaces whereby each of said surfaces isinhibited against corrosion; and (e) allowing said condensed distillateto return to said hydrocarbon processing unit, or to be collected assaid product.
 13. A process as claimed in claim 12, wherein said streamincludes crude oil, feedstock, and hydrocarbon stream and/or fractionsthereof.